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Pengjin Qin Li-An Wang Prof. Joseph M. O'Connor Prof. Kim K. Baldridge Yifan Li Burak Tufekci Jiyue Chen Prof. Arnold L. Rheingold 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(41):18114-18121
Triene 6π electrocyclization, wherein a conjugated triene undergoes a concerted stereospecific cycloisomerization to a cyclohexadiene, is a reaction of great historical and practical significance. In order to circumvent limitations imposed by the normally harsh reaction conditions, chemists have long sought to develop catalytic variants based upon the activating power of metal–alkene coordination. Herein, we demonstrate the first successful implementation of such a strategy by utilizing [(C5H5)Ru(NCMe)3]PF6 as a precatalyst for the disrotatory 6π electrocyclization of highly substituted trienes that are resistant to thermal cyclization. Mechanistic and computational studies implicate hexahapto transition-metal coordination as responsible for lowering the energetic barrier to ring closure. This work establishes a foundation for the development of new catalysts for stereoselective electrocyclizations. 相似文献
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Chemical versus Electrochemical Synthesis of Carbon Nano‐onion/Polypyrrole Composites for Supercapacitor Electrodes
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Olena Mykhailiv Monika Imierska Martyna Petelczyc Prof. Dr. Luis Echegoyen Dr. Marta E. Plonska‐Brzezinska 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(15):5783-5793
The development of high‐surface‐area carbon electrodes with a defined pore size distribution and the incorporation of pseudo‐active materials to optimize the overall capacitance and conductivity without destroying the stability are at present important research areas. Composite electrodes of carbon nano‐onions (CNOs) and polypyrrole (Ppy) were fabricated to improve the specific capacitance of a supercapacitor. The carbon nanostructures were uniformly coated with Ppy by chemical polymerization or by electrochemical potentiostatic deposition to form homogenous composites or bilayers. The materials were characterized by transmission‐ and scanning electron microscopy, differential thermogravimetric analyses, FTIR spectroscopy, piezoelectric microgravimetry, and cyclic voltammetry. The composites show higher mechanical and electrochemical stabilities, with high specific capacitances of up to about 800 F g?1 for the CNOs/SDS/Ppy composites (chemical synthesis) and about 1300 F g?1 for the CNOs/Ppy bilayer (electrochemical deposition). 相似文献
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Dr. Sabin Llona‐Minguez Dr. Matthieu Desroses Artin Ghassemian Dr. Sylvain A. Jacques Dr. Lars Eriksson Rebecka Isacksson Tobias Koolmeister Dr. Pål Stenmark Dr. Martin Scobie Prof. Thomas Helleday 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(20):7394-7398
A two‐step synthesis of structurally diverse pyrrole‐containing bicyclic systems is reported. ortho‐Nitro‐haloarenes coupled with vinylic N‐methyliminodiacetic acid (MIDA) boronates generate ortho‐vinyl‐nitroarenes, which undergo a “metal‐free” nitrene insertion, resulting in a new pyrrole ring. This novel synthetic approach has a wide substrate tolerance and it is applicable in the preparation of more complex “drug‐like” molecules. Interestingly, an ortho‐nitro‐allylarene derivative furnished a cyclic β‐aminophosphonate motif. 相似文献
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Interactions of Pt‐ttpy with G‐Quadruplexes Originating from Promoter Region of the c‐myc Gene Deciphered by NMR and Gel Electrophoresis Analysis
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Qin Yin Shou-Guo Wang Xiao-Wei Liang De-Wei Gao Jun Zheng Shu-Li You 《Chemical science》2015,6(7):4179-4183
An organocatalytic asymmetric chlorinative dearomatization of naphthols was realized for the first time, providing chiral naphthalenones with a Cl-containing all-substituted stereocenter in excellent yields and enantioselectivity (up to 97% yield and 96% ee). The reaction features mild reaction conditions, good tolerance of diverse functional groups and simple reaction operation. 相似文献
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Pd0‐Catalyzed Intramolecular α‐Arylation of Sulfones: Domino Reactions in the Synthesis of Functionalized Tetrahydroisoquinolines
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Prof.Dr. Daniel Solé Ferran Pérez‐Janer Dr. Raffaella Mancuso 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(12):4580-4584
A new strategy for the synthesis of tetrahydroisoquinolines based on the Pd0‐catalyzed intramolecular α‐arylation of sulfones is reported. The combination of this Pd‐catalyzed reaction with intermolecular Michael and aza‐Michael reactions allows the development of two‐ and three‐step domino processes to synthesize diversely functionalized scaffolds from readily available starting materials. 相似文献
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讨论一类非齐次非线性椭圆边界值问题.利用极大值原理证明了该问题解的梯度估计.作为它的应用得到了解的效率比估计. 相似文献